Antistatic agent and coating or molding synthetic resins

ABSTRACT

The object of the present invention is to provide an antistatic agent used for thermoplastic resin having aromatic ring(s) such as a styrene group resin, polyester resin, or the like A graft copolymer whose main chain is acrylic rubber and graft chain is of a polymer chain mainly consisting of a styrene group monomer or copolymer chain mainly consisting of a styrene group monomer and nitrile group monomer is used as said antistatic agent. Besides said graft copolymer, antistatic properties are is given to said thermoplastic resin by blending said thermoplastic resin with a compound having a hydrophilic group so as to be a blend polymer or a polymer alloy. Further, antistatic properties are given to a resin molded article by coating it with a paint containing hydrophilic polymer.

FIELD OF THE INVENTION

The present invention relates to an antistatic agent which is mainlymixed into synthetic resin for molding or in paint, to prevent theelectrification of molded article. Further, the present inventionrelates to a synthetic resin compound used for molding or in paint.

BACKGROUND OF THE INVENTION

Hitherto, as an antistatic agent, which is mixed into a synthetic resinfor molding, a surface active agent, containing such as carboxylic acidsalt, sulfonic acid salt (see for example Patent Literature 1),quaternary ammonium salt (see for example Patent Literature 2),phosphate, or the like, and an inorganic compound, such as carbon block(see for example Patent Literatures 3 and 4), metal oxide (see forexample Patent Literature 5), alkaline metal salt (see for examplePatent Literature 6) and the like, have been used.

Patent Literature 1

-   -   Publication Tokkaihei 10-287814

Patent Literature 2

-   -   Publication Tokkaihei 6-100522

Patent Literature 3

-   -   Publication Tokkaihei 7-207141

Patent Literature 4

-   -   Publication Patent 2663592

Patent Literature 5

-   -   Publication Tokkaihei 9-183865

Patent Literature 6

-   -   Publication Patent 3060127

Patent Literature 7

-   -   International Publication WO 00/5384

Patent Literature 8

-   -   Publication Tokkai 2002-105332

Said surface active agent has faults in that it is apt to bleed out ofthe surface of the molded article, so that said antistatic surfaceactive agent has a poor durability, and further, in a case where scrapsof a molded article containing said surface active agent areincinerated, it is feared that poisonous gas will be produced.

Further, in a case where said surface active agent is added to theresin, it is also feared that properties of the resin, such as waterresistance, chemical resistance, mechanical strength and the like willbe degraded

Further, in a case of the resin, into which rubber in whose main chainunsaturated bond(s) is (are) contained (such as butadiene group rubber)is compounded (such as ABS, HIPS, modified PPE), the physical propertiesof the resin may degrade remarkably in repeated recycles (see forexample Patent Literatures 7 and 8).

Said inorganic compounds as described above, such as carbon block, metaloxide, and the like, are effectively antistatic when said inorganiccompounds are used in a large amount, but since said inorganic compoundshave incompatibility with the resin to which said inorganic compoundsare added, said inorganic compounds retard the fluidity of the meltingof the resin when said inorganic compounds are added to the resin in alarge amount, degrading its moldability. Further, since carbon or metaloxide colors the resin molded article, so that it may be difficult tocolor said resin molded article as desired.

DISCLOSURE OF THE INVENTION

To solve the aforementioned problems of the prior art, the presentinvention provides an antistatic agent made of one or a mixture of twoor more kinds selected from a group consisting of a graft copolymer,whose main chain is an acrylic rubber and graft chain is of a polymerchain mainly consisting of a styrene group monomer or a copolymer chainmainly consisting of a styrene group monomer and nitrile group monomer,a block copolymer consisting of acrylic rubber block(s) and styrenegroup polymer block(s), or styrene group and nitrile group copolymerblock(s), a cellulose derivative except nitrocellulose, a phosphoricester compound, polyester, polycarbonate, phatalic acid ester, andadipic acid ester.

Commonly, said antistatic agent is added to thermoplastic resin havingaromatic ring(s), and in this case, said thermoplastic resin havingaromatic ring(s) may be a styrene group resin, polyester resin,polyphenylene ether resin or polycarboneite resin.

Further, the present invention provides a synthetic resin used in paintor for molding, containing 5 to 50% by mass of a graft copolymer, whosemain chain is an acrylic rubber, and graft chain is of a polymer chainmainly consisting of styrene group monomer, or a copolymer chain mainlyconsisting of a styrene group monomer and nitrile group monomer as anantistatic agent, or a synthetic resin compound used in paint or formolding containing 5 to 50% by mass of a block copolymer containingacrylic rubber block(s), and polymer block(s) mainly consisting of astyrene group monomer or copolymer block(s) mainly consisting of astyrene group monomer and nitrile monomer as an antistatic agent.

Still further, the present invention provides a synthetic resin compoundused in paint or for molding containing 5% by mass of a cellulosederivative except nitrocellulose as an antistatic agent.

Still further, the present invention provides a synthetic resin compoundused in paint or for molding containing 5 to 35% by mass of a phosphoricester compound as an antistatic agent.

Still further, the present invention provides a synthetic resincompound, used in paint or for molding, containing 5 to 35% by mass ofan antistatic agent made of a mixture of a graft copolymer, whose mainchain is an acrylic rubber and graft chain is of a polymer chain mainlyconsisting of a styrene group monomer or a copolymer chain mainlyconsisting of a styrene group monomer and nitrile group monomer, andphosphoric ester, wherein said graft copolymer and said phosphoric esterare mixed in a mass ratio in the range of between 10:90 and 50:50, or asynthetic resin compound, used in paint or for molding, containing 5 to35% by mass of an antistatic agent made of a mixture of a blockcopolymer consisting of acrylic rubber block(s), and polymer block(s)mainly consisting of a styrene group monomer or copolymer block(s)mainly consisting of a styrene group monomer and nitrile monomer, andphosphoric ester, wherein said block copolymer and said phosphoric esterare mixed in a mass ratio in the range of between 10:90 and 50:50.

Commonly, said synthetic resin is a thermoplastic resin having aromaticring(s), and in this case said thermoplastic resin having aromaticring(s) may be a styrene group resin, polyester resin, polyphenyleneether resin or polycarbonate resin.

(Action)

Said graft copolymer whose main chain is an acrylic rubber and graftchain is of a polymer chain mainly consisting of a styrene group monomeror a copolymer chain mainly consisting of a styrene group monomer andnitrile group monomer as an antistatic agent, or said block copolymerconsisting of acryl rubber block(s) and styrene group polymer block(s)or styrene group and nitrile group copolymer block(s) as an antistaticagent, has compatibility with the objective synthetic resin,particularly having a polymer chain the same as or similar to a polymerchain mainly consisting of a styrene group monomer, or a styrene groupmonomer and nitrile group monomer, and said antistatic agent isuniformly mixed into said resin, to exercise its durable antistaticeffect. Further, said antistatic agent does not separate from saidresin, so that said antistatic agent does not degrade the mechanicalstrength of said resin. Said antistatic agent of the present invention,containing an acrylic rubber as a main component, has excellentflexibility and durability, so that in a case where said antistaticagent is added to said resin, its mechanical properties such as impactresistance may be improved. Further, said antistatic agent containing anacrylic rubber has a good heat stability, so that the antistatic effectand rubber-like properties, and the like, are maintained in saidantistatic agent after repeated recyclings.

(Effect of the Invention)

Said antistatic agent of the present invention prevents theelectrification of the objective resin without degrading its mechanicalproperties, such as impact resistance and the like.

PREFERED EMBODIMENT

The present invention is described precisely below.

The polymer used in said antistatic agent is an acrylic rubber. Saidacrylic rubber may be such as a homopolymer of acrylic ester, whosealkyl group has desirably 2 to 8 carbon atoms, said acrylic ester beingsuch as ethyl acrylate, n-butyl acrylate, 2-ethyl-hexyl acrylate and thelike, or a copolymer of two or more kinds of said acrylic ester togetheror a copolymer of one or more kind(s) of said acrylic ester(s), and oneor more kind(s) of other monomer(s), such as butadiene or anon-conjugated diene compound such as dicyclopentadiene,tricyclopentadiene, 5-methyl-2,5-norbornadiene,5-methylene-2-norbornene, 5-vinyl-2-norbornene,5-ethylidene-2-norbornene, 5-isopropylidene-2-norbornene,5-isopropenyl-2-norbornene, 5-(1-butenyl)-2-norbornene,5-(2-propenyl)-2-norbornene, 5-(5-hexenyl)-2-norbornene,4,7,8,9-tetrahydro-indene, isopropylidenetetrahydroindene-indene,cyclooctadiene, vinylcyclohexene, 1,5,9-cyclododecatoluene,6-methyl-4,7,8,9-tetrahydroindene, 2,2′-dicyclopentenyl,trans-1,2-divinylcyclobutane, 1,4-hexadiene, 2-methyl-1,4-hexadiene,1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene,3,6-dimethyl-1,7-octadiene, 4,5-dimethyl-1,7-octadiene,1,4,7-octatriene, 5-methyl-1,8-nonadiene and the like, acrylonitrile,methyl methacrylate, vinyl acetate, styrene, ethylene, propylene and thelike, and further said copolymer includes a copolymer of one or morekind(s) of said acrylic ester(s) and one or more kind(s) of othermonomer(s) such as a monomer having a functional group, said monomerbeing such as an acrylic acid, methacrylic acid, β-hydroxyethylmethacrylate, acrylamide, dimethylaminoethyl methacrylate and the like,a polymerizable silane coupling agent such asγ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane,p-trimethoxysilylstyrene, p-triethoxysilylstyrene,p-trimethoxysilyl-α-methylstyrene, p-triethoxysilyl-α-methylstyrene,γ-acryloxypropyltrimethoxysilane, vinyltrimethoxysilane,N-β(N-vinylbenzylaminoethyl-γ-aminopropyl)trimethoxysilane hydrochlorideand the like.

As a general purpose acrylic rubber may be such as polyn-butyl acrylate,polyethyl acrylate in which a few monomer(s) having functional group asdescribed above is(are) copolymerized, n-butyl acrylate-acrylonitrilecopolymer, n-butyl acrylate-butadiene copolymer, n-butylacrylate-ethylene copolymer, n-butylacrylate-γ-methacryloxypropyltrimethoxysilane copolymer, n-butylacrylate-vinyltrimethoxysilane copolymer and the like, and a preferableacrylic rubber is n-butyl acrylate-butadiene copolymer whose molar ratioof n-butyl acrylate/butadiene is 70/30 or higher. Commonly, said acrylicrubber is produced by suspension polymerization, emulsionpolymerization, or the like. A styrene group monomer or styrene groupmonomer and nitrile group monomer is(are) graft copolymerized, and/orblock copolymerized, and/or random copolymerized, to/with said acrylicrubber, to give compatibility with the objective resin, particularlyhaving structure the same as or similar to polymer chain mainlyconsisting of a styrene monomer, or styrene monomer and nitrile monomer.

Said styrene group monomer graft copolymerized, and/or blockcopolymerized, and/or random copolymerized, to/with said acrylic rubber,is such as styrene, α-alkylmonovinylidene aromatic monomer (for example,α-methylstyrene, α-ethylstyrene, α-methyl vinyl toluene,α-methyldialkylstyrene and the like), nuclear substituted alkylstyrene(for example, o-, m- or p-vinyltoluene, o-ethylstyrene, p-ethylstyrene,2,4-dimethylstyrene, p-t-butylstyrene and the like), nuclear substitutedhalostyrene (for example, o-chlorostyrene, p-chlorostyrene,o-bromostyrene, 2,4-dichlorostyrene and the like), a nucleic substitutedstyrene with an alkyl group and halogen (for example,2-chloro-4-methylstyrene, 2,6-dichlorostyrene and the like),vinylnaphthalene, vinylanthracene and the like, and said styrene groupmonomer may be used alone or a mixture of two or more kinds of saidstyrene monomer(s) may be used. Generally, an alkyl substituent has 1 to4 carbon atoms, and includes both linear and branched alkyl groups.

Nitrile monomer which is graft copolymerized and/or block copolymerizedand/or random copolymerized to/with said acrylic rubber together withsaid styrene group monomer is such as methacrylonitrile,ethacrylonitrile, fumaronitrile and the like and a mixture of two ormore kinds of said nitrile group monomers.

In addition to said styrenic monomer and said nitrile monomer, othermonomers such as olefin group monomer such as ethylene, propylene,ethylene-vinyl acetate copolymer and the like, diene group monomer suchas isoprene, chloroprene, butadiene and the like, vinyl ether groupmonomer such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinylether, n-butyl vinyl ether and the like may also be copolymerized.

As said antistatic agent of the present invention, polyester representedby such as a polyethylene terephthalate (PET), polybutyleneterephthalate (PBT) and polybutylene naphthalate (PEN), polycarboxylicacid ester represented by polycarbonate (PC), polyamide resin, EVA orEEA, ethylene vinyl alcohol copolymer (EVOH), thermoplastic polyurethaneelastomer made of polyester or polyether as raw material, polyestergroup or polyamide group thermoplastic elastomer, a biodegradable resinsuch as polylactic acid, a highly water absorbent resin represented bysuch as ARASOAP, KI gel, Aquakeep, Lanseal, F AQUAPEARL (all being tradenames) and the like.

In addition, as the antistatic agent of the present invention, thecompound described below may be used. Said compound may be a phosphateor phosphorus compound such as tricresyl phosphate, diphenylcresylphosphate, trioctyl phosphate, tributyl phosphate, triphenyl phosphate,tris(chloroethyl) phosphate, tris(monochloropropyl) phosphate,tris(dichloropropyl) phosphate, triallyl phosphate,tris(3-hydroxypropyl) phosphineoxide, tris(tribromo) phosphate, trisβ-chloropropyl phosphate, tris(dibromophenyl) phosphate,tris(tribromoneopentyl) phosphate, tetrakis(2-chloroethyl) phosphinate,dimethylethyl phosphinate tris (2-chloroethyl) o-phosphate, aromaticcondensed phosphate (for example, PX-200, CR-733S, CR-735, DaihachiChemical Industry Co., Ltd.), a halogen-containing condensed phosphate(for example, CR-505, CR509, CR-512, CR-380, CR-504, CR-507, CR-387,CR-106 and the like, Daihachi Chemical Industry Co., Ltd.),ethylene-bis-tris(2-cyanoethyl)phosphonium bromide, ammoniumpolyphoshate, β-chloroethyl acid phosphate, β-chloropropyl phosphate,butyl prophosphate, butyl acid phosphate, butoxyethyl acid phosphate,2-ethylhexyl acid phosphate and the like, a melamine phosphate such asmelamine phosphate, dimelamine phosphate, melamine borate, melaminecyanulate and the like, a phosphate (for example, K-19A, Mobil Chem), aphosphorus compound, a halogen-containing compound such asdibromoneopentyl glycol, 2,4,6-tribromophenol, tribromophenylallylether, tetrabromobisphenol A derivative (for example, Fire Guard 3000,3100, 3200, 7000, 7500 and the like, Teijin, ANFLAME FSB-330, FSB-310and the like, NOF Corporation, BA-50, BA-50P and the like, Great LakesChem.), tetrabromobisphenol S, tris-(2,3-dibromopropyl-1)-isocyanulate,poly(pentabromobenzyl/acrylate), tribromophenyl maleimide,tribromoneopentyl alcohol, tetraburomodipentaerythritol,pentabromobenzyl acrylate, pentabromophenol, pentaburomodiphenyl oxide,pentabromodiphenyl ether, octabromophenyl ether, octabromodiphenylether, octabromodiphenyl oxide, magnesium hydroxide, dibromoneopentylglycol tetracarbonate, bis(tribromophenyl)phthalmaleimide,N-methylhexabromodiphenylamine, a halogen-containing phosphate, abrominated epoxy (for example, SR-SB, SR-TBA350, SR-TBA400, SR-TBA400T,SR-TNA400M, T-20000 and the like, Sakamoto Yakuhin Kogyo Co., Ltd.,EPICHLON 152, 160, 165, 1120, Dainippon Ink Co., Ltd., BROMRITE BR-128,BR-156, BR-133, BR-140, BR343, Hitachi Chemical Co., Ltd, EBR-700,EBR-107, EB-242MT, EB-300, MANAC, F-2000, F-2300, F-2310, F-2400,F-2300H, F-2400E, F-2001, Dead Sea Bromine) and the like; CREINDICanhydride, tetrabromophthalic anhydride, tetrabromobisphenol A,diethoxy-bis-(2-hydroxyethyl)amnomethyl phosphate, dibromocresylglycidylether, dibromophenol, dibromocresol, tribromophenol, phenyl phosphinicacid, phenylphosphinic dichloride, diethylphenyl phosphnate,dimethylphenyl phosphonate and the like. Generally any of theseantistatic agents is used together with an antimony oxide such as anantimony trioxide, sodium antimonate, an inorganic compound such asaluminum hydroxide, magnesium hydroxide and zinc borate and the like.Further, as said antistatic agent of the present invention, the compounddescribed below may be used. Said compound may be such as a phthalicacid derivative, such as, dimethyl phthalate, diethyl phthalate, higheralcohol a phthalate, diisooctyl phthalate, benzyl phthalate, butylbenzylphthalate, diisononyl phthalate, dinormalalkyl phthalate and the like, atetrahydrophthalic acid derivative, an adipic acid derivativerepresented by such as dibutyl adipate, diethyl adipate, diisodecyladipate, diisobutyl adipate, diisononyl adipate, diisooctyl adipate,dibutyl diglycol adipate and di-n-alkyl adipate, an azelaic acidderivative represented by such as a di-n-hexyl azelate, dimethylazelate, dibenzyl azelate and the like, a sebacic acid derivativerepresented by such as di-n-butyl sebacate, dimethyl sebacate,dibutoxyethyl sebacate and the like, a dodecane diacid derivative, amaleic acid derivative represented by such as di-n-butyl maleate,dimethyl maleate and the like, a fumaric acid derivative represented bysuch as di-n-butyl fumarate, a trimellitic acid derivative representedby such as triisodecyltrimellitate, triisooctyl trimellitate and thelike, and additionally a pyromellitic acid derivative, citric acidderivative, itaconic acid derivative, oleic acid derivative, stearicacid derivative, or fatty acid derivative represented by such aspolyethylene glycol 200 monolaurate, polyethylene glycol 400monolaurate, aliphatic dibasic acid ester and the like, a sulfonic acidderivative represented by such as a phenolic alkyl sulfonate,N,N-benzeneslfonamide and the like, a phosphoric acid derivativerepresented by such as trimethyl phosphate, triethyl phosphate, tributylphosphate, tri(2-ethylhexyl)phosphate, triphenyl phosphate,diisodecyldiphenyl phosphate, tricresyl phosphate, trixylenyl phosphate,alkylallyl phosphate, tetrakis(2,4-di-t-butylphenyl)-4,4′-biphenylenediphosphonate and the like, a gurtaric acid derivative represented bysuch as didecyl gurtarate, dibutoxyethyl gurtarate and the like, amonoester represented by such as dipentaerythritol, aliphaticmonocarboxylate and the like, a glycol derivative represented by such aspolyethylene glycol, polyethylene glycol benzoate, a glyceric acidderivative represented by such as glycerol monoacetate, glyceroldiacetate, glycerol triacetate and the like, a polyester grouprepresented by such as adipic acid polyester, a sebacic acid-basedpolyester, adipic acid-1,3-butylglycol-based substance (for example,BAA-15 Daihachi Chemical Industry Co., Ltd.), polyester sebacate,polyether, ether thioether, ester thioester, stearic acid esteramide,phthalic acid-based ester and the like, further, a metal salt of aphosphite or stearic acid phosphate, an ester of amino acid andcarboxylic acid and polyhydric acid, a benzenesulfonic acid salt ofalkaline metal, an alkaline earth metal or other metals, montanic acidester montanic acid salt of alkaline metal, alkaline earth metal orother metals, a stearic acid salt of alkaline metal, alkaline earthmetal or other metals, a hydroxystearic acid, n-butyl stearate, apolyhydric alcohol fatty acid ester, a saturated fatty acid ester, anaromatic alcohol fatty acid ester, a higher alcohol, a higher alcoholester (RIKEN VITAMINE, Henkel), a partial ester of a polyhydric alcoholwith a fatty acid such as glycerin fatty acid ester stearic acidmonoglyceride, linolic acid monoglyceride, carboxylate, a condensate ofa fatty acid salt with a polyether, a sorbitan fatty acid ester, a fattyacid diethanolamide, methylmethacrylate butadiene styrene resin, anEVA-PVC-graft copolymer, acrylic resin, vinyl acetate-ethylene copolymerresin, xylene formaldehyde resin, a maleic anhydride modifiedpolybutadiene resin, a compatibility aid agent (for example, MODIPERA4100, A5100, A6100, A8100, A1200, A4200, A5200, A6200, A8200, A4400,A5400, A6400, A8400, NOF Corporation), sodium polyacrylate, sodiumpolycarboxylate, alkylallyl sulfonate (for example, sodiumdodecylbenzene sulfonate, sodium alkyldiphenylether disulfonate,alkylbenzene sulfonate, dodecylbenzene sulfonic acid amine salt and thelike), a formalin condensate of alkylallylsulfonate,alkylsulfosuccinate, alkylsuofate salt, pentachlorophenol, a cellulosederivative (for example, cellulose nitrate, cellulose acetate, celluloseacetate acetate, methylcellulose methylhydroxyethyl cellulose,methylhydroxypropyl cellulose, hydroxyethyl cellulose and the like), amodified sodium polyacrylate, an ammonium polyacrylate, a partiallysaponified polyacrylate, a sodium polyacrylate/polyacrylic acid amidecopolymer, a polyacrylamide, a carboxylated styrene butadiene polymer, acarboxylated vinyl polymer, a methylene vinyl ether maleic anhydridecopolymer, a polyvinyl alcohol, a polyethylene glycol monostearate, apolyethylene glycol distearate, a polyethlene alkyl ether derivative andthe like.

[Objective Resin]

The objective resin, into which said antistatic agent is added may beany kind of thermoplastic resin. A desirable thermoplastic resin is onehaving the same or a similar structure as/to a polymer chain consistingmainly of a styrene group monomer, or styrene group monomer and nitrilegroup monomer, and said thermoplastic resin may be such as a styrenegroup resin, polyphenylene ether group resin, polycarbonate resin,polyester resin, each of said resins having aromatic ring(s).

[Styrenic Group Resin]

The styrenic group resin of the present invention is one containing atleaset more than 25% by mass of a styrene group monomer, said resin mayinclude a homopolymer of a styrene group monomer or a copolymer of twoor more kinds of styrene group monomer together, a copolymer of one ormore kind(s) of styrene group monomer(s), and one or more kinds of themonomer(s) being copolymerizable with said styrene group resin, or agraft copolymer, in which one or more kind(s) of styrene groupmonomer(s) is (are) graft polymerized to a diene group rubber.

Further, said styrene group resin of the present invention includes amicroblend or polymer blend of said styrene group resin and diene groupresin and/or olefine group rubber and/or acrylic rubber.

A typical styrene group resin may be such as polystyrene(PS) which ishomopolymer of styrene, high impact polystyrene(HIPS) which is a polymerblend of polystyrene and a rubbery polymer in which styrene is graftpolymerized to a diene group rubber, acryronitrile/styrene copolymer(AS), styrene/butadiene copolymer, styrene/α-methylstyrene copolymer,styrene/maleic anhydride copolymer, styrene/methylmethacrylatecopolymer, styrene/ethylene copolymer,styrene/ethylene/propylene/butadiene copolymer, ABS which is blendpolymer of acrylonitrile-styrene copolymer and a graft polymer in whichacrylonitrile and styrene are graft polymerized to butadiene rubber, ACSwhich is a resin mixture of chlorinated polyethylene andacrylonitrile-styrene copolymer, AES which is a resin mixture ofacrylonitrile-styrene copolymer and acrylenitrile-styrene terpolymercontaining an olefine group rubber in which acrylonitrile and styreneare graft polymerized to said olefine group rubber, AAS which is a resinmixture of acrylonitrile-styrene copolymer and acrylonitrile-styreneterpolymer containing an acrylic rubber in which acrylonitrile andstyrene are graft polymerized to acrylic rubber, ASiS which is a resinmixture of acrylonitrile-dimethylsiloxane-styrene copolymer andacrylonitrile butadiene-styrene copolymer.

[Polyphenylene Ether (PPE) Group Resin]

A typical PPE group resin of the present invention is poly(2,6-dimethyl-1,4-phenylene ether) produced by the oxidativepolymerization of 2,6-xylenol with a copper a catalyst and further saidPPE group resin of the present invention includes copolymer of2,6-dimethyl-1,4-phemylene ether and 2,3,6-trimethyl-1,4-phenyleneether, and a copolymer of 2,6-dimethylphenol 2,3,6-trimethylphenol andthe like.

Still further, said PPE group resin of the present invention includes amodified PPE produced by the modification of said PPE group resin with astyrene group resin and/or amide group resin.

[Polycarbonate Resins (PC Resins)]

In the present invention, polycarbonate resin is singly used alone as amolding material or used as a polymer alloy or polymer blend by mixingit with said styrene group resin, PPE group resin, or the like.

Any kind of polycarbonate derived from an aromatic dihydroxy compoundmay be used as said PC resin (aromatic PC resin) of the presentinvention.

As said aromatic dihydroxy compound, for instance,2,2-bis(4-hydroxyphenyl)propane (also referred to as bisphenol A),tetramethylbisphenol A, tetrabromobisphenol A,bis(4-hidroxyphenyl)-p-diisopropylbenzene, hydroquinone, resorcinol,4,4′-dihydroxydiphenyl and the like, may be used, though generallybis(4-hydroxy phenyl) alkane group dihydroxy compound is selected, butbisphenol A, in particular, or combination of bisphenol A and anotheraromatic dihydroxy compound is preferable.

[Polyester Resin]

The polyester resin of the present invention is such as polybutyleneterephthalate(PBT), polyethylene terephthalate(PET) and the like.

Said antistatic agent of the present invention is generally added tosaid objective resin in an amount of between 0.1 and 85% by mass, butpreferably between 1 and 40% by mass.

In a case of an antistatic agent, which is a graft co-polymer havingacrylic rubber as its main chain and a polymer chain mainly consistingof a styrene group monomer or a styrene group monomer and nitrile groupmonomer as its branch part, said antistatic agent is preferablycontained in resin for paint, or resin for molding, in an amount ofbetween 5 and 50% by mass.

Further, in a case of an antistatic agent, which is a block copolymercontaining acrylic rubber block(s) and polymer block(s) mainlyconsisting of a styrene group monomer or copolymer block(s) mainlyconsisting of a styrene group monomer and nitrile group monomer, saidantistatic agent is preferably contained in resin for paint, or resinfor molding, in an amout of between 5 and 50% by mass.

Said antistatic agent of the present invention may be used by adding itto paint. In a case where paint containing said antistatic agent iscoated on a molded article, dust and the like are less likely attach topart(s) being coated with said paint, as well as the surrounding areasof said parts being coated.

In a case where said paint containing said antistatic agent of thepresent invention is coated on a molded article of said objective resin,acrylic resin or styrene modified acrylic resin is preferably used as apaint vehicle.

Said acrylic resin is a copolymer containing acrylic acid ester, andsaid styrene modified acrylic resin is a copolymer of styrene andacrylic acid ester.

Said acrylic acid ester, may include such as methyl acrylate, ethylacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate,isobutyl acrylate, t-butyl acrylate, 2-ethyl hexyl acrylate, cyclohexylacrylate, tetrahydrofurfuryl acrylate and the like.

Further, methacrylate such as methyl methacrylate, ethyl methacrylate,n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate,isobutylmethacrylate, 2-ethylhexyl methacrylate, cyclohexylmethacrylate, tetrahydrofurfuryl methacrylate, stearyl methacrylate,lauryl methacrylate or the like may be used in said acrylic resin.

In said styrene modified acrylic resin, other monomer(s) may becopolymerized in such an amount that the resulting resin does not losecompatibility with the thermoplastic resin of the molded article, andthe like.

Other monomers described above may be such as vinyl ether such asmethylvinyl ether, ethylvinyl ether, n-propylvinyl ether, n-butylvinylether, isobutylvinyl ether and the like, a nitrile-based monomer such asacrylonitrile, methacrylonitrile and the like, an aliphatic vinyl suchas vinyl acetate, vinyl propionate and the like, an olefin such asethylene, propylene and the like, a diene such as isoprene, chloroprene,butadiene and the like, an α, β-unsaturated carboxylic acid such asacrylic acid, methacrylic acid, itaconic acid, maleic acid, crotonicacid, atropic acid, citraconic acid and the like, hydroxylgroup-containing monomer such as 2-hydroxylethyl methacrylate,2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxtpropylacrylate, allylalcohol and the like, an amide such as acrylamide,methacryklamide, diacetone acrylamide and the like, aminogroup-containing monomer such as dimethylaminomethyl methacrylate,dimethylaminoethyl methacrylate, dimethylaminopropyl acrylate and thelike, epoxy group-containing monomer such as glycidyl acrylate, glycidylmethacrylate, glycidyl ether and the like, hydrolytic silylgroup-containing vinyl monomer such as γ-methacryloxypropyltrimethoxysilane, vinylacetoxy silane, p-trimethoxysilylstyrene,p-triethoxysilylstyrene, p-trimethoxysilyl-α-methylstyrene,p-triethoxysilyl-α-methylstyrene, γ-acryloxypropyltrimethoxysilane,vinyltrimethoxysilane,N-β(N-vinylbenzylaminoethyl-γ-aminopropyl)trimethoxysilane hydrochlorideand the like.

Said monomer may be used alone or two or more kinds of monomer(s) may beused together.

Further, a mixture of two or more kinds of paint vehicles which are ofthe same kind but each have different molecular weights may be used.

Said antistatic agent used as an additive in paint may be such as acellulose and its derivative, such as methyl cellulose, ethyl cellulose,hydroxy cellulose, hydroxypropylmethy cellulose, hydroxyethylmethylcellulose, acetic acid cellulose, cellulose acetate, acetyl cellulose,benzyl cellulose, cellulose acetate butyrate (CAB), cellulose nitrate(NC) or the like.

Said antistatic agent may be used alone or two or more kinds of saidantistatic agent may be used together.

The optimum viscosity for the dispersion of said cellulose acetatebutylate(optimum viscosity for the preparation of paint) is in the rangeof between 0.1 and 0.55 sec., a lower viscosity than said optimumviscosity being caused by an excess of solvent. On the other hand, ahigher viscosity than that of said optimum viscosity causes a problem inthat cellulose acetate butylate is hard to disperse well.

Further, the acetyl group content of said cellulose acetate butylate ispreferably in the range of between 0 and 15%. As the content of saidacetyl group becomes greater, its grease resistance, tensile strength,hardness, melting point, and specific gravity rise accordingly. On theother hand, the optimum content of said butyryl group is in the range ofbetween 30.0 and 55.0%. A higher content of said butyryl group than saidoptimum content improves solubility, dilution resistance, compatibility,softness and water resistance.

Said cellulose acetate is cellulose diacetate, and the acetylationdegree of said cellulose acetate is in the range of between 50 and 60%,but preferably between 54 and 56%. In this range of said acetylationdegree, said cellulose diacetate is soluble in an ester group solvent,ketone group solvent, a hi-solve acetate, and halogenated hydro carbon,said cellulose diacetate being easily dissolved in solvent during paintpreparation.

The ethoxy group content of said ethyl cellulose is preferably in therange of between 45 and 50%. In a case where the ethoxy group content iswithin said range, said ethylcellulose has compatibility with the resinused in paint or printing ink.

The methoxy group content of said methyl cellulose is preferably in therange of between 19 and 31.5%. In a case where the methoxy group contentis within said range said methylcellulose has high surface activity,excellent protective ability for hydrophobic colloid, and excellentability to stabilize both suspension and emulsion.

The hydroxylpropoxy group content of said hydroxylpropylmethyl celluloseis preferably in the range of between 4 and 12%. In a case when thehydroxyl propoxy group content is within said range, saidhydroxylpropylmethyl cellulose has excellent salt resistance, PHresistance and enzyme resistance.

The hydroxylethoxy group content of said hydroxylethylmethyl celluloseis preferably in the range of between 4 and 12%.

In a case where the hydroxy ethoxy group content is within said range,said hydroxylethyl methyl cellulose has excellent salt resistance, PHresistance, and enzyme resistance. Further, the viscosity of 2% by massaqueous solution of said hydroxylethyl cellulose is in the range ofbetween 20 and 100000 cps(mPa·s).

In a case where cellulose acetate butylate is used in paint as anantistatic agent, pellets prepared by smashing a molded article ontowhich a coating film containing said cellulose acetate butylate iscovered, and then pelletizing said smashed molded article by heating andmelting, may not yellow.

An additional amount of said antistatic agent is set to be more than 5%by mass, but preferably 15% by mass in dry film. In a case where theaddition amount of said antistatic agent is less than 5% by mass in saiddry film, antistatic effect can not be expected.

In said antistatic agent of the present invention, a pigment, dye,reinforcing agent (glass fiber, carbon fiber and the like), filler(carbon black, silica, titanium oxide, talc and the like), heatresistant agent, anti-aging agent, an antioxidant, antiozonant,weatherproof (light stabilizing) agent (UV absorber, light stabilizer),plasticizer, foaming agent, foaming aid agent, lubricant, internalreleasing agent, releasing agent, hazing proof agent, crystallinenucleus agent, flame retardant, flame retardation aid agent, fluiditymodifier, compatibility aid agent or the like may be added in such anamount that the effect of said antistatic agent is not lost.

[Synthetic Resin for Paint or Molding]

A synthetic resin for paint or molding prepared by adding said staticagent of the present invention into said objective resin has excellentantistatic properties.

As said synthetic resin, a synthetic resin having an aromatic ring(s) ispreferable. Said synthetic resin having an aromatic ring(s) is such as astyrene group resin, polyester resin, polyphenylene ether resin,polycarbonate resin and the like.

In a case where a cellulose derivative is contained in said syntheticresin for paint or molding as an antistatic agent, the content of saidcellulose derivative is preferably in the range of between 5 and 35% bymass.

Further, in a case where phosphate is contained in said synthetic resinfor paint or molding as antistatic agent, the content of said phosphateis preferably in the range of between 5 and 35% by mass.

The present invention is described below by EDXAMPLE. However, it is tobe understood that the invention is not intended to be limited to thespecific examples.

EXAMPLE 1

An acrylonitrile-styrene-graft-acrylic rubber(AnSt-g-acrylic rubber) wasprepared by graft polymerizing acrylonitrile and styrene(20:80 massratio) to an acrylic rubber, which is a copolymer of n-butylacrylate andbutadiene(80:20 mass ratio) (EXAMPLE 1).

Fifteen parts by mass of the resulting antistatic agent was added to 100parts by mass of AS resin, and a resin molded article was manufactured.The resulting resin molded article was kept in a room for six months,after which the situation of dust, speck and the like contamination onsaid resin molded article was optically observed. The result is shown inTable 1. In Table 1, X shows a situation where dust and the likeattached to said molded article, ◯ shows a situation where dust and thelike attached to said molded article in a relatively small amount.

For COMPARISON, the situations of dust and the like contamination onresin molded articles to which an acrylonitrile-styrene-graft-butadienerubber(AnSt-g-butadiene rubber) in which acrylonitrile and styrene aregraft-polymerized to a butadiene rubber(COMPARISON 1) and anacrylonitrile-styrene-graft-ethylene-propylene-diene rubber(AnSt-g-EPDM) in which acrylonitrile and styrene are graft-polymerizedto an ethylene-propylene-diene rubber (EPDM) (COMPARISON 2) were eachadded, were also observed under the same conditions as in EXAMPLE 1. Theresults are shown in Table 1. TABLE 1 Situation of Objective dust andthe Antistatic agent resin like contamination Example 1 AnSt-g-Acrylicrubber AS ∘ Comparison 1 AnSt-g-butadiene AS x rubber Comparison 2AnSt-g-EPR AS xIt was recognized that said resin molded article in which AuSt-g-acrylicrubber was added to AS resin (AAS resin molded article) showed betterantistatic properties than said resin molded articles in whichAnSt-g-butadiene rubber and AuSt-G-EPR were each added to AS resin (ABSresin molded article, AES resin molded article).

EXAMPLE 2

Styrene-graft-acrylic rubber (St-g-acrylic rubber) was prepared by graftpolymerizing styrene to an acrylic rubber, which is a copolymer ofn-butylacrylate and acrylic acid(99:1 mass ratio)(EXAMPLE 2). Ten partsby mass of the resulting antistatic agent was added to 100 parts by massof PS and PPE respectively, to manufacture resin molded articles. Theresulting resin molded articles were each kept in a room for six months,after which, the situations of dust, speck, and the like contamination,were optically observed. The result is shown in Table 2. In Table 2, Xshows a situation where dust and the like attached to said moldedarticles, while ◯ shows a situation where dust and the like attached tosaid molded articles in a relatively small amount. For COMPARISONS, thesituations of dust and the like contamination on resin molded articlesto which a styrene graft-butadiene rubber(St-g-butadiene rubber)(COMPARISON 3) in which a styrene is graft polymerized to a butadienerubber, and a styrene-g-graft-ethylene propylene rubber(St-g-EPR)(COMPARISON 4) in which styrene is graft polymerized to an ethylenepropylene-rubber were each added, were optically observed under the sameconditions as in EXAMPLE 2. The results are shown in Table 2. TABLE 2situation of dust Objective and the like Antistatic agent resincontamination Example 2 St-g-Acrylic rubber PS ∘ St-g-Acrylic rubber PPE∘ Comparison 3 St-g-butadiene rubber PS x St-g-butadiene rubber PPE xComparison 4 St-g-EPR PS x St-g-EPR PPE xIt was recognized that HIPS and modified PPE resin molded articles, toeach of which St-g-acrylic rubber was added, each have superiorantistatic properties to resin molded articles in which St-g-butadienerubber and St-g-EPR were added respectively.

Further, it was confirmed that in a case where the acrylic rubbercontent in said antistatic agent was increased from 10% to 20%, theamount of dust and the like contamination was smaller as compared withthe case of the 10% addition.

EXAMPLE 3

A paint A containing a styrene modified acrylic resin as its vehicle, apaint B containing CAB, and a paint C containing NC, were each coated onone side of an ABS molded article, having a size of 250 mm(W)×250mm(L)×2 mm(thickness), each thickness being 15 μm. The resulting moldedarticles with coated paints A, B, and C were each kept in a room for sixmonths, after which the situations of dust, speck, and the likecontamination on said molded articles were optically observed, toconfirm that a comparatively small amount of dust and the like attachedto said molded articles with coated paints A, B, and C, in comparisonwith ABS molded article being uncoated, (Evaluated as ┌◯┘) for eachmolded articles coated with paints A, B, and C.

[Reference 1]

Resin pellets were manufactured by compounding 20% by mass ofAnSt-g-acrylic rubber of EXAMPLE 1 in AS resin, melting and mixing theresulting compound, and then pelletizing it. The resulting resin pelletswere held in the heating cylinder of the injection molding machine at250° C. for one hour to exert thermal stress, after which the impactstrength of said resin on which said thermal stress was exerted wasdetermined.

As a result, assuming that the Izod impact strength of the virgin resinwas 100, the Izod impact strength of said resin on which the thermalstress was exerted was 97 as a relative value, confirming that saidresin has high heat stability, and said resin can be recycledrepeatedly.

Thermal stress was exerted on ABS resin the same as described above, andin this case, the relative value of the Izod impact strength decreasedto 46; ABS resin, containing 20% by mass of polyether ester amide as ahydrophilic polymer, which is a commercial antistatic agent (PELESTAT NC6321 (trade name), SANYO CHEMICAL, INDUSTRIES, Ltd.) had thermal stressexerted on it at 259° C. for one hour, and its Izod impact strengthdecreased to 19; and a resin prepared by adding 20% by mass ofAnSt-g-acrylic rubber to said AS resin, then melting and mixing it, andadding 20% by mass of PELESTAT NC 6321, had thermal stress exerted on itthe same as described above, and in this case, the relative value of itsIzod impact strength decreased to 21. From these results, it wascomfirmed that in a case where PELESTAT NC 6321 is added to a resinhaving good recycling properties (a resin containing AnSt-g-acrylicrubber), the heat stability of the resulting resin degrades, so that aresin to which polyether ester amide is added, to give it permanentantistatic properties, has poor recycling properties.

About Commercial resins, PALEL (trade name, Toray) and ADION (tradename, A&M STYRENE STYREME Co.) to which polyether ester amide is added,to give them permanent antistatic properties, the same heating andmelting test was performed, and as a result, a remarkable degradation inthe physical properties of each resin was recognized, showing poorrecyclability.

[Reference 2]

Molded articles coated with paint A, paint B, and paint C in EXAMPLE 3were each smashed, and pelletized, and re-molded to confirm the effectthe of coating films contamination, and as a result, recycled resins, inwhich paint A and paint B, are each contaminated, have relative valuesof Izod impact strength 98 for paint A, and 97 for paint B respectively,demonstrating that each recycled resin has excellent heat stability.

About paint C, its relative value of Izod impact strength is 94, butdiscoloration (browning) of said resin was confirmed, proving thatNitrocellulose(NC) has poor heat stability.

EXAMPLE 4

Molded articles respectively made of polymer alloys PET/ABS=50/50,HIPS/PET=50/50, PC/ABS=75/25, PC/PS=75/25, EVA/ABS=70/30, EEA/ABS=80/20,ABS/PELPRENE P-150-B (trade name)=40/60, and PA-6/PPE=60/40, and furthermolded articles made of PC, PA-6, PET, and PBT were kept in a room forsix months the same as in EXAMPLE 1, after which the situations of dust,speck, and the like contamination were optically observed for eachmolded article. As a result of this observation, a relatively smalleramount of dust and the like contaminated each molded article, incomparison with ABS and HIPS into which no hydrophilic resins wereblended, so that it was evaluated as ┌◯┘.

EXAMPLE 5

Twenty % by mass of an antistatic agent consisting of an aromaticcondensed phosphoric acid ester (PX-200 (trade name), DAIHACHI CHEMICALINDUSTRY Co., Ltd.) was added to both ABS and HIPS, and resin moldedarticles were manufactured. The resulting resin molded articles wereeach kept in a room for six months, the same as in EXAMPLE 1, and thesituations of dust, speck, and the like contamination for each resinmolded article were optically observed.

For COMPARISONS resin molded articles made of only ABS and only HIPSwere each kept in a room for six months, the same as described above toobserve optically the situations of dust, speck, and the likecontamination for each resin molded article. As a result of theobservations it was recognized that a relatively smaller amount of dustand the like attached to the molded articles containing any kind ofantistatic agent, in comparison with the molded articles containing noantistatic agent.

EXAMPLE 6

Fifteen % by mass of an antistatic agent, tetrabromobisphenol Aderivative (Fire Guard, 3100, TEIJIN CHEMICALS Ltd.), was added to ASresin and PS resin respectively, to manufacture resin molded articles.The resulting resin molded articles were each kept in a room for sixmonths, the same as in EXAMPLE 1, after which the situations of dust,speck, and the like contamination on each molded article were opticallyobserved. For COMPARISONS resin molded articles made of only AS resinand only PS resin were each kept in a room for six months the same asdescribed above, to observe optically the situations of dust, speck andthe like contamination on each molded article.

As a result of the observations, a relatively smaller amount of dust,specks, and the like attached to said molded articles containing anantistatic agent, in comparison with said molded articles made of ASresin without an antistatic agent, and PS resin also without anantistatic agent.

EXAMPLE 7

Fifteen % by mass of an antistatic agent, bromide epoxy (SR-T 20000,SAKAMOTO YAKUHIN KOGYO CO., LTD.), was added to both AS resin and PSresin, and resin molded articles were manufactured. The resulting resinmolded articles were each kept in a room for six months, the same as inEXAMPLE 1, after which the situations of dust, speck and the likecontamination on each molded article were optically observed. ForCOMPARISONS, resin molded articles made of only AS resin and only PSresin were each kept in a room for six months, the same as describedabove, to observe the situations of dust speck, and the likecontamination on each resin molded article.

A comparatively smaller amount of dust and the like attached to anymolded article containing an antistatic agent, in comparison with moldedarticles made of AS resin without an antistatic agent, and PS resin alsowithout an antistatic agent.

EXAMPLE 8

The cabinet of a xerographic machine (PPC) made of ABC resin (CYCOLAC,XFJ-5, UMG ABS Ltd.) was smashed and washed by a flushing crusher(Plassholie, TANAKA Ltd.) to obtain smashed material, said xerographicmachine being withdrawn from the market, 2% by mass or 4% by mass ofAnSt-g-acrylic rubber were each added to the resulting smashed material,and recycled pellets were manufactured by melting and mixing in atwin-screw extruder (TECHNOBEL). Using the resulting recycled pellets,molded articles were respectively manufactured by injection molding.

On the other hand, 12 parts by mass parts of an antistatic agent(PX-200) was added to 100 parts by mass of said recycled pellets, afterwhich pellets were manufactured by melting and mixing. A molded articlewas manufactured by injection molding the resulting pellets. The amountof dust and the like contamination on each molded article was estimated.The results are shown in Table 3. TABLE 3 Additional amount of AnSt-g-AR(% by mass) 2 4 2 4 PX-200 (parts by mass) 0 0 12 12 Evaluation of dustadhesion (after being x x ∘ ∘ kept for six months in a room)

EXAMPLE 9

Using an acrylonitril-estyrene-graft-ethylene propylene diene rubber(AnSt-g-EPDM wherein DM is DCP, ethylene-propylene ratio=75:26) insteadof the AnSt-g-acrylic rubber of EXAMPLE 8, an evaluation test the sameas in EXAMPLE 8 was performed. The results are shown in Table 4. Furtherthe results concerning a molded article made of only recycled ABS arealso described in Table 4. TABLE 4 Additional amount of AnSt-g-EPDM (%by mass) 2 4 2 4 0 PX-200 (parts by mass) 0 0 12 12 0 Evaluation of dustx x ∘ ∘ x adhesion (after being kept for six months in a room)

EXAMPLE 10

The St-g-acrylic rubber of EXAMPLE 2, being 28.6% by mass, was added tothe PS resin pellets, to produce HIPS pellets.

Further, 8 to 12 parts by mass of an antistatic agent (PX-200) was mixedinto 100 parts by mass of the resulting HIPS pellets, and a moldedarticle was manufactured by heating and melting in said twin screwextruder. The adhesion of dust and the like on each molded article wasevaluated. The results are shown in Table 5. TABLE 5 PX-200 (parts bymass) 0 8 10 12 Evaluation of dust adhesion (after being ∘ ∘ ∘ ∘ keptfor six months in the room)

EXAMPLE 11

Thirty five % by mass of PET resin pellets were mixed into the ABS resinpellets of EXAMPLE 8, and a molded article A was manufactured bymolding, using said mold from EXAMPLE 3. The resulting molded article Awas coated with paint A (dry film thickness 5 μm) and then with paint B(dry film thickness 5 μm), paints A and B being used in EXAMPLE 3, and acoated molded article B was manufactured.

The resulting coated molded article B was smashed, pelletized andremolded, to manufacture a molded article C. Paint D (35% by mass of CABbeing added to paint A to prepare paint D) was coated on the resultingmolded article C to manufacture a molded article D.

The amount of dust and the like contamination on each molded article A,B, C, and D was evaluated after said molded articles had been kept in aroom for six months. For a COMPARISON, the amount of dust and the likecontamination on a molded article made of only ABS resin was alsoevaluated.

The amount of dust and the like contamination on each molded article A,B, C, and D was comparatively smaller, when compared with that of saidmolded article made of only ABS resin, and it was recognized that saidmolded articles A, B, C, and D have an antistatic effect. The reasonswhy the above described results were obtained, are considered to bebecause of the existence of PET resin in molded article A, the existenceof CAB in the coating film in molded article B, the existence of PET andCAB in molded article C, and the existence of CAB in the coating film inmolded article D.

EXAMPLE 12

Five % by mass of AnSt-g-acrylic rubber of EXAMPLE 1 was added and mixedinto said recycled material (ABS resin) of EXAMPLE 8, and further, anantistatic agent (PX-200) was added in amounts of 0, 8, 10, 12, and 14%by mass respectively and the resulting mixtures were melted and conbinedto manufacture pellets.

The resulting pellets were respectively molded to manufacture moldedarticles. The amount of dust and the like contamination on each moldedarticle after being kept in a room for six months was evaluated. Theresults are shown in Table 6. TABLE 6 Recycled material AnSt-g-AR (ABS)(Added at 5% by mass) PX-200 0 0 8 10 12 14 (parts by mass) Dustadhesion x Δ ∘ ∘ ∘ (after being kept for six months in a room)

EXAMPLE 13

Using the AnSt-g-EPDM of EXAMPLE 1 instead of the AnSt-g-acrylic rubberof EXAMPLE 12, molded articles were manufactured to be the same as inEXAMPLE 12, in order to evaluate the mount of dust and the likecontamination on each molded article. The results are shown in Table 7.TABLE 7 Recycled material AnSt-g-EPSM (ABS) (Added at 5% by mass) PX-2000 0 8 10 12 14 (parts by mass) Dust adhesion x x ∘ ∘ ∘ ∘ (after beingkept for six months in a room)

EXAMPLE 14

Forty parts by mass parts of the AnSt-g-acrylic rubber of EXAMPLE 1, 20parts by mass of AS resin, and 40 parts by mass of PS 200 were meltedand strongly kneaded by an external heating type kneader, and theresulting mixture was pelletized to prepare a master batch A, ofantistatic agent. A master batch B, was prepared by using a mixture ofAnSt-g-acrylic rubber/AS/PX-200=50/15/35 using the same method asdescribed above. Twenty parts by mass parts of said master batches A andB were both added to said recycled material of EXAMPLE 8, and aftermolding, the resulting molded articles were each kept in a room for sixmonths, after which the amount of dust and the like contamination oneach molded article was evaluated. The amount of dust and the likecontamination on said molded articles to which master batches A and Bwere each added was clearly small, and evaluated as ┌◯┘ (The evaluationstandard is the same as in the above described EXAMPLES).

EXAMPLE 15

Using the same composition, with the exception that St-g-acrylic rubberwas used instead of the AnSt-g-acrylic rubber of EXAMPLE 14, the sameevaluation as in EXAMPLE 14 was performed. The amount of dust and thelike contamination was small, the same as in EXAMPLE 14, and evaluatedas ┌◯┘.

INDUSTRIAL UTILITY

Said antistatic agent of the present invention is usable in resin formolding or for paint.

1. An antistatic agent made of one or a mixture of two or more kindsselected from a group consisting of a graft copolymer, whose main chainis an acrylic rubber and graft chain is of a polymer chain mainlyconsisting of a styrene group monomer or a copolymer chain mainlyconsisting of a styrene group monomer and nitrile group monomer, a blockcopolymer consisting of acrylic rubber block(s) and styrene grouppolymer block(s), or styrene group and nitrile group copolymer block(s),a cellulose derivative except nitrocellulose, a phosphoric estercompound, polyester, polycarbonate, phatalic acid ester, and adipic acidester.
 2. An antistatic agent according to claim 1, wherein saidantistatic agent is added to thermoplastic resin having aromaticring(s).
 3. An antistatic agent according to claim 2 wherein saidthermoplastic resin having aromatic ring(s) is a styrene group resin,polyester resin, polyphenylene ether resin or polycarbonate resin.
 4. Asynthetic resin used in paint or for molding containing 5 to 50% by massof a graft copolymer, whose main chain is an acrylic rubber and graftchain is of a polymer chain mainly consisting of a styrene group monomeror a copolymer chain mainly consisting of a styrene group monomer andnitrile group monomer as an antistatic agent.
 5. A synthetic resincompound used in paint or for molding containing 5 to 50% by mass of ablock copolymer containing acrylic rubber block(s), polymer block(s)mainly consisting of a styrene group monomer or copolymer block(s)mainly consisting of a styren group monomer and nitrile group monomer asantistatic agent.
 6. A synthetic resin compound used in paint or formolding containing 5% by mass of cellulose derivative exceptnitrocellulose as an antistatic agent.
 7. A synthetic resin compoundused in paint or for molding containing 5 to 35% by mass of a phosphoricester compound as an antistatic agent.
 8. A synthetic resin compoundused in paint or for molding, containing 5 to 35% by mass of anantistatic agent made of a mixture of a graft copolymer, whose mainchain is an acrylic rubber and graft chain is of a polymer chain mainlyconsisting of a styrene group monomer or a copolymer chain mainlyconsisting of a styrene group monomer and nitrile group monomer, andphosphoric ester, wherein said graft copolymer and said phosphoric esterare mixed into a mass ratio in the range of between 10:90 and 50:50. 9.A synthetic resin compound, used in paint or for molding, containing 5to 35% by mass of an antistatic agent made of a mixture of a blockcopolymer consisting of acrylic rubber block(s), and polymer block(s)mainly consisting of a styrene group monomer or copolymer blocks mainlyconsisting of a styrene group monomer and nitrile group monomer, andphosphoric ester, wherein said block copolymer and said phosphoric esterare mixed in a mass ratio in the range of between of 10:90 and 50:50.10. A synthetic resin compound used in paint or for molding according toclaim 4, wherein said synthetic resin is thermoplastic resin havingaromatic ring(s).
 11. A synthetic resin compound used in paint or formolding according to claim 10 wherein said thermoplastic resin havingaromatic ring(s) is a styrene group resin, polyester resin,polyphenylene ether resin or polycarbonate resin.
 12. A synthetic resincompound used in paint or for molding according to claim 5, wherein saidsynthetic resin is thermoplastic resin having aromatic ring(s).
 13. Asynthetic resin compound used in paint or for molding according to claim6, wherein said synthetic resin is thermoplastic resin having aromaticring(s).
 14. A synthetic resin compound used in paint or for moldingaccording to claim 7, wherein said synthetic resin is thermoplasticresin having aromatic ring(s).
 15. A synthetic resin compound used inpaint or for molding according to claim 8, wherein said synthetic resinis thermoplastic resin having aromatic ring(s).
 16. A synthetic resincompound used in paint or for molding according to claim 9, wherein saidsynthetic resin is thermoplastic resin having aromatic ring(s).